Deposit control additives based on hydrazine

ABSTRACT

Liquid hydrocarbon distillate fuel compositions are provided comprising a hydrocarbonaceous distillate fuel boiling in a gasoline range containing an aliphatic hydrocarbon substituted hydrazine. The aliphatic hydrocarbon radical is relatively free of aliphatic unsaturation and is of from about 400-5,000 molecular weight. The hydrazines useful in preparing the compounds of this invention may be mono- or di-substituted on one of the nitrogens, while the second nitrogen must have at least one hydrogen atom present prior to reaction with the aliphatic hydrocarbon.

United States Patent [1 1 Coon [ Mar. 25, 1975 [75] Inventor: Marvin D. Coon, Novato, Calif.

[73] Assignee: Chevron Research Company, San

Francisco, Calif.

[22] Filed: Mar. 15, 1973 [21] Appl No.: 341,622

Related [1.8. Application Data [62] Division of Ser. No. 130,770, April 2, 197l.

[52] US. Cl. 44/64, 252/50 [5]] Int. Cl C10] 1/22 [58] Field of Search 44/64; 252/50 [56] References Cited UNITED STATES PATENTS 2,971,828 2/l96l Churchill et al. 44/64 2,975,136 3/l96l Thomas et al. 44/64 FOREIGN PATENTS OR APPLICATIONS 572,478 3/1959 Canada 44/64 Primary Examiner-Daniel E. Wyman Assistant ExaminerY. H. Smith Attorney, Agent, or Firm-G. F. Magdeburger; C. J. Tonkin; M. D. Nelson [57] ABSTRACT Liquid hydrocarbon distillate fuel compositions are provided comprising a hydrocarbonaceous distillate fuel boiling in a gasoline range containing an aliphatic hydrocarbon substituted hydrazine. The aliphatic hydrocarbon radical is relatively free of aliphatic unsaturation and is of from about 4005,000 molecular weight. The hydrazines useful in preparing the compounds of this invention may be monoor disubstituted on one of the nitrogens, while the second nitrogen must have at least one hydrogen atom present prior to reaction with the aliphatic hydrocarbon 10 Claims, No Drawings DEPOSITCONTROL ADDITIVES BASED ON HYDRAZINE This is a division of application Ser. No. 130,770, filed Apr. 2, 1971.

BACKGROUND OF THE INVENTION 1. Field of the Invention Distillate fuels, such as gasoline and jet fuels, are compounded with a variety of additives. Recently, there has been a concerted effort to provide detergent additives which act to maintain the valves and manifold ports in a clean condition. Because of the detergent nature of these additives, water tolerance problems have often arisen. By water tolerance is intended the rate of separation after agitation, between the aqueous phase and the organic phase, and the retention of water in the organic phase, so that as to retain a hazy appearance. Many of these detergents require the use of some form of a demulsifier to improve the water tolerance to a level where the detergent, otherwise very useful, can satisfactorily pass water tolerance tests.

This invention is directed toward detergent additives and the combination of these detergent additives with distillate fuels. The subject detergent additives, while maintaining their detergent nature, in some cases, have excellent water tolerance in the absence of any demulsifier and where a demulsifier is required, only a minimal amount is necessary.

SUMMARY OF THE INVENTION Liquid hydrocarbon distillate fuel compositions are provided comprising a hydrocarbonaceous distillate fuel boiling in a gasoline range containing an aliphatic hydrocarbon substituted hydrazine. The aliphatic hydrocarbon radical is relatively free of aliphatic unsaturation and is of from about 400 to 5,000 molecular weight. The hydrazines useful in preparing the compounds of this invention may be monoor disubstituted on one of the nitrogens, while the second nitrogen must have at least one hydrogen atom present prior to reaction with the aliphatic hydrocarbon.

The compounds are also contemplated as part of this invention.

DETAILED DESCRIPTION OF THE INVENTION The compositions which find use in this invention will for the most part have the following formula:

The above symbols are defined as follows:

R an aliphatic hydrocarbon radical of from about 400 to 5,000 average molecular weight.

X hydrogen, methyl, and ethyl Y hydrogen, phenyl, tolyl, hydrocarbyl of from 1 to 4 carbon atoms; -CI-I CH(CH )OH, CH C- HZOH, --CH2CH2OCH3, and

Z hydrogen, phenyl, tolyl, hydrocarbyl of from 1 to 4 carbon atoms; CH CH(CH )OH, CH C- H OH, --CH CH OCH and CH CH OCH CH The tolyl radical may have the methyl group attached at the ortho, meta, or para position.

The hydrocarbon radical indicated by R is relatively free of aliphatic unsaturation; that is, it will usually have not more than two sites of olefinic unsaturation and generally not more than one site of olefinic unsaturation and no acetylenic unsaturation.

The aliphatic hydrocarbon radical will ordinarily be prepared by polymerizing olefins of from 2 to 6 carbon atoms (ethylene being copolymerized with another olefin so asbto provide a branched chain). The branched chain hydrocarbon radical will generally have at least 1 branch per 6 carbon atoms along the chain, preferably at least 1 branch per 4 carbon atoms along the chain and particularly preferred that there be at least 1 branch per 2 carbon atoms along the chain. That is, the preferred branch chain hydrocarbon radicals are polypropylene and polyisobutylene. The branches will be of from 1 to 2 carbon atoms usually, preferably 1 carbon atom, i.e., methyl.

In most instances, the compositions of this invention are not a pure single product, but rather a mixture of compounds having an average molecular weight. Usually, the range of molecular weights will be relatively narrow and peaked near the indicated molecular weight.

Synthesis The compositions of this invention are readily prepared by combining an aliphatic or alicyclic halide with the desired hydrazine in the proper mole proportions. The halide is prepared from the hydrocarbon by halogenation: ionically or free radically.

As already indicated, the hydrocarbon groups may be prepared by ionic or free radical polymerization of olefins of from 2 to 6 carbon atoms (ethylene must be copolymerized with another olefin) to an olefin of the desired molecular weight. The olefins which find use are ethylene, propylene, isobutylene, l-butene, l-pentene, 3-methyll-pentene, 4-methyl-l-pentene, etc., preferably propylene and isobutylene.

As previously indicated, there should be at least 1 branch per 6 carbon atoms along the chain and preferably at least 1 branch per 4 carbon atoms along the chain. The preferred olefins, propylene and isobutylene, have from 0.5 to 1 branch per atom along the hydrocarbon chain.

The halogen may be introduced into the hydrocarbon molecule by various means known in the art. Most readily, either chlorine or bromine (halogen of atomic number 17-35) may be introduced by the free radical catalyzed halogenation of the hydrocarbon, or ionic ad dition to olefinic unsaturation. Various free radical catalysts may be used, such as peroxides, azo compounds, bromine, iodine, as well as light. Ionic catalysts are exemplified by ferric chloride. Methods of halogenation are well known in the art and do not require extensive exemplfication or illustration here.

The amount of halogen introduced will depend on the particular hydrocarbon used, the desired amount of the hydrazine (the hydrazine being used herein to include the substituted hydrazines as well as unsubstituted hydrazines) to be introduced into the molecule, the particular hydrazine used, and the halogen used. The amount of halogen introduced will generally be in the range from about 1 to 5 halogen atoms per molecule, depending on the reactivity of the resulting halide. On a weight percent basis, the amount of halide will generally range from about 1 to 25, more usually from about 1 to 10.

The halohydrocarbon and the hydrazine may be brought together neat or in the presence of an inert solvent, particularly a hydrocarbon solvent. The inert hydrocarbon solvent may be aliphatic or aromatic. Also, aliphatic alcohols may be used by themselves or in combination with another solvent, when capable of dissolving the reactants.

The reaction may be carried out at temperatures ranging from about 80 to 200C, preferably from 140 to 170C. Depending on the temperature of the reaction, the particular halogen used, the mole ratios and the particular hydrazine, as well as the reactant concentrations, the time may vary from 1 to 24 hours, more usually from about 3 to 10 hours. Times greatly in excess of 24 hours do not particularly enhance the yield and may lead to undesirable degradation. It is therefore preferred to limit the reaction time to fewer than 24 hours.

The mole ratio of halohydrocarbon to the hydrazine will generally be in the range from about 0.5 to 10 moles of the hydrazine per mole of halohydrocarbon, more usually 2 to 4 moles of the hydrazine per mole of halohydrocarbon. The mole ratio will depend upon the amount of halogen present in the halohydrocarbon, the particular halogen and the desired ratio of hydrocarbon to the hydrazine. 1f complete suppression of polysubstitution of the hydrazine is desired, then large mole excesses of the hydrazine will be used where necessary, i.e., when more than one hydrogen is available for reaction on the hydrazine.

Small amounts of residual halogen in the final composition are not deleterious. Generally, the residual halogen as bound halogen will be in the range of to weight percent of the composition. Small amounts of halogen may be present as the hydrohalide salt of the hydrocarbon substituted hydrazine.

Generally, the hydrocarbons used will have aliphatic unsaturation. In particular instances, the hydrazines may react in a way resulting in the elimination of hydrogen halide, introducing further aliphatic unsaturation into the hydrocarbon radical. Therefore, the hydrocarbon radicals usually will be olefinically unsaturated. However, the olefinic unsaturation does not significantly affect the utility of the product, and when available, saturated aliphatic halide may be used.

After the reaction has been carried out for a sufficient length of time, the reaction mixture may be extracted with hot or cold water to free the product from any low molecular weight hydrazine salt which has formed. The product may then be isolated by evaporation of the solvent. Further separation from unreacted hydrocarbon or purification may be carried out as desired, e.g., chromatography, vacuum stripping, etc.

Depending on the particular application of the composition of this invention, the reaction may be carried out in the medium in which it will ultimately find use and be formed at concentrations which provide a concentrate of the detergent compositon. Thus, the final mixture may be in a form to be used directly upon dilution in fuels where excess amounts of the hydrazine or low molecular weight hydrazine salts will not be deletenous.

The detergent will generally be employed in a hydrocarbon base liquid fuel. The detergent additive may be formulated as a concentrate, using a suitable hydrocarbon alcohol solvent boiling in the range of about 150 to 400F. Preferably, an aromatic hydrocarbon solvent is used, such as benzene, toluene, xylene or higher boiling aromatics or aromatic thinners. Aliphatic alcohols of about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, n-butanol and the like, in combination with hydrocarbon solvents are also suitable for use with the detergent additive.

ln gasoline fuels, other fuel additives may also be included such as antiknock agents, e.g., tetramethyl lead or tetraethyl lead. Also included may be lead scavengers such as aryl halides, e.g., dichlorobenzene or alkyl halides, e.g., ethylene dibromide.

A nonvolatile lubricating mineral oil, e.g., petroleum spray oil, particularly a refined naphthenic lubricating oil having a viscosity of 100F. of 1,000 to 2,000 SUS, is a suitable additive for the gasoline compositions used with the detergents of this invention and its use is preferred. These oils are believed to act as a carrier for the detergent and assist in removing and preventing deposits. They are employed in amounts from about 0.05 to 0.5 percent by volume, based on the final gasoline composition.

In the fuel the concentration of the detergent will generally be at least 100 ppm and usually not more than 4,000 ppm, more usually in the range of from about 200 to about 800 ppm. ln concentrates, the detergent will generally be from 1 to 50 weight percent, more usually from about 5 to 30 weight percent.

The following examples are offered by way of illustration and not by way of limitation.

EXAMPLE 1 Chlorinated polyisobutylene (100 g, 0.071 mole) of rnw 1,400 having a chlorine content of 4.18 percent was dissolved in 100 ml of benzene. Phenylhydrazine (15.1 g, 0.14 mole) was added in one shot, and the solution heated to reflux with stirring. The solvent was distilled at atmospheric pressure until the temperature rose to 160C. Heating and stirring were continued for 4 hours. Toluene (100 ml) and n-butanol (25 ml) were added and the resulting solution washed three times with 100 ml portions of hot water containing 5 percent n-butanol. The solution was concentrated by distillation and stripped on a solvent stripper under vacuum (5 mm) at about C. to yield g of polyisobutylene phenylhydrazine: N, 0.97; Cl, 1.05; mw 1,480.

' EXAMPLE 2 Chlorinated polyisobutylene g, 0.071 mole) as described in Example 1 was dissolved in 100 ml of benzene. Hydroxyethylhydrazine (20.9 g, 0.29 mole) was added. The solvent was removed by distillation at atmospheric pressure until the temperature reached C. Heating was continued for 3 hours, followed by workup as described in Example 1 to yield 90 g of polyisobutylene hydroxethylhydrazine: N, 1.01; Cl, 1.61; mw 1,860.

EXAMPLE 3 Chlorinated polyisobutylene (100 g, 0.071 mole) as described in Example 1 and unsymmetrical dimethylhydrazine (17.4 g, 0.29 mole) were dissolved in 50 ml of benzene. Solvent was removed by distillation at atmospheric pressure until the temperature reached C. The solution was cooled to 90C and 6 ml more dimethylhydrazine was added, followed by heating at reflux (160C) f or 3 hours. The mixture was worked up as in Example 1 to yield 91 g of polyisobutylene dimethylhydrazine: N, 1.03; Cl, 1.63, mw 1,680.

EXAMPLE 4 Chlorinated polyisobutylene (100 g, 0.071 mole) as described in Example 1 was dissolved in 50 ml of benzene and 100 ml of n-butanol. The solution was heated to 65C. and hydrazine (85 percent, 9.8 g, 0.29 mole) was added. The temperature was increased to 85C. and 35 ml more of benzene added. The solution was maintained at reflux with stirring for 2 hours. The solvent was then removed by distillation at atmospheric pressure until the temperature reached 160C. More hydrazine (3 ml) was added, causing the temperature to drop to 145C. Heating was continued for l-Vz hours. The solution was then allowed to stand at room temperature overnight, followed by a further l- /2 hours of heating at reflux the next day. n-Butanol (50 ml) was added and solvent removed by distillation at atmospheric pressure until the temperature increased to 190C. The solution was cooled; 100 ml of toluene and 25 ml of n-butanol was added, followed by washing first with 100 ml of 5 percent NaOH, then twice with 100-ml portions of hot water. The solution was concentrated by distillation at atmospheric pressure, then stripped on a solvent stripper at about 80C. under vacuum (5 mm). Benzene (approximately 100 ml) was added, followed by further stripping on the solvent stripper to give 87 g of polyisobutylene hydrazine: N, 0.85; Cl, 1.06; mw 1,934.

The polyisobutylene hydrazines of Examples 1-4 were tested for detergency in a Waukesha ASTM-CPR single-cylinder engine having the specifications set forth in Table 1. The conditions of the test were specified in Table 2.

TABLE 1 Compression ratio 9-1 Bore 3.25 inches Stroke 4.5 inches Displacement 37.33 cubic inches TABLE 2 Engine speed 1 800 rpm Duration of test 12 hours Engine jacket temp. 212F.

Continued Engine manifold vacuum 15-inch Hg lntake air temp 95F. Air/fuel ratio 14 Ignition spark timing 15 BTC Base fuel used ASTM distillation starting point,

ll5F.. 208F. distilled. 907! at 354F.,

end point 415F.,

research octane 85 8.

The weight of the deposits on the intake valve were determined after washing with hexane. The results shown in Table 3 were obtained.

TABLE 3 Wt in mg of Deposit Additive* After Washing with Hexane Example 1 reaction product 40 Example 2 reaction product 21 Example 3 reaction product 34 Example 4 reaction product 24 Mixture of Hydrazines from Runs 1, 2, 3; Ratio 413:3

Base Gasoline Containing 1,000 ppm of Zerolene 9 84 (Average of 3 Runs) A mixture of 300 ml of gasoline containing the additive, and 3 ml of synthetic sea water was blended in a Waring Blender for 30 seconds at 13,500 rpm. The blended mixture was poured into lpint bottles, and the bottles rated at the end of four hours using the following system: excellent, clear fuel phase and clear mobile water on the bottom (essentially like base fuel containing no additives); good, mobile water phase with a hazy fuel phase; fair, milky, or cloudy water phase with little free mobile water and a very hazy fuel phase; poor, very cloudy water phase, no free water droplets, fuel phase very hazy. Mobile is defined as distinct water droplets which move back and forth on the bottom of the bottle when the bottle is slowly rocked.

Table 4 lists the results of the blender test with and without added demulsifier. The phenylhydrazine com- 50 pound sheds water even without a demulsifier present at 400 ppm and the other hydrazines respond very well to the demulsifier. A concentration study (see Table 5) shows that the phenylhydrazine has good water tolerance properties up to a concentration of 800 ppm and in the presence of demulsifier as high as 3,200 ppm (the highest concentration studied).

TABLE 4 Ratings for Waring Blender Tests on the Various Hydrazine Derivatives at 400 ppm Additive Concentration added and additional blending 7 TABLE Ratings for Waring Blender Tests on the Phenylhydrazine Derivative of Ex. I at Various Concentrations An ethyleneoxy modified alkylphenol-formaldehytle polymer having an average of live :ilkylphennl groups and an average of six ethyleneoxy groups per phenol. The alkyl group has rm average of eight carbon atoms.

X i N wherein R is polyisobutylene or polyisopropylene radical of from about 400 to 5,000 average molecular weight; X is hydrogen, methyl, and ethyl; Y is hydrogen, phenyl. tolyl, hydroearbyl of from I to 4 carbon atoms, CH CH(CH ,)OH, CH C- H, CH2CH2OCH3, and

Z is hydrogen, phenyl, tolyl, hydroearbyl of from 1 to 4 carbon atoms, CH CH(CH )OH, CH C- H OH, CH CH OCH and CH CH OCH CH with the proviso that said tolyl may have the methyl group attached at the ortho, meta, or para position.

2. The composition of claim 1 wherein X is hydrogen, Y is hydrogen and Z is phenyl.

3. The composition of claim 2 wherein R is polyisobutylene of about 1,400 average molecular weight.

4. The composition of claim 1 wherein X is hydrogen, Y is hydrogen and Z is CH CH OH.

5. The composition of claim 4 wherein R is polyisobutylene of about L400 average molecular weight.

6. The composition of claim 1 wherein X is hydrogen Y is methyl and Z is methyl.

7. The composition of claim 6 wherein R is polyisobutylene of about 1,400 average molecular weight.

8. The composition of claim 1 wherein X is hydrogen. Y is hydrogen and Z is hydrogen.

9. The composition of claim 8 wherein R is polyisobutylene of about 1,400 average molecular weight.

10. The composition of claim 1 having from 0.05 to 0.5 percent by volume of a mineral lubricating oil. 

1. A FUEL COMPOSITION HAVING A MAJOR AMOUNT OF A HYDROCARBONACEOUS DISTILLATE FUEL BOILING IN THE GASOLINE RANGE AND IN AN AMOUNT TO PROVIDE DETERGENCY AND DISPERSANCY, A COMPOSITION OF THE FORMULA:
 2. The composition of claim 1 wherein X is hydrogen, Y is hydrogen and Z is phenyl.
 3. The composition of claim 2 wherein R is polyisobutylene of about 1,400 average molecular weight.
 4. The composition of claim 1 wherein X is hydrogen, Y is hydrogen and Z is -CH2CH2OH.
 5. The composition of claim 4 wherein R is polyisobutylene of about 1,400 average molecular weight.
 6. The composition of claim 1 wherein X is hydrogen, Y is methyl and Z is methyl.
 7. The composition of claim 6 wherein R is polyisobutylene of about 1,400 average molecular weight.
 8. The composition of claim 1 wherein X is hydrogen, Y is hydrogen and Z is hydrogen.
 9. The composition of claim 8 wherein R is polyisobutylene of about 1,400 average molecular weight.
 10. The composition of claim 1 having from 0.05 to 0.5 percent by volume of a mineral lubricating oil. 